Hydrocarbon oil hydrotreating method

SUBSTANCE: invention is related to hydrocarbon oil hydrotreating method using at least the first and second reactors. The method includes (i) contacting of hydrocarbon oil in the first reactor at high temperature and pressure with hydrotreating catalyst in presence of hydrogen-containing gas wherein hydrogen is consumed; (ii) division of the outgoing flow obtained at the stage (i) into partially hydrotreated hydrocarbon oil and contaminated hydrogen-containing gas by means of a steam stripper, wherein the waste hydrogen-containing gas is used as stripping gas; (iii) contacting of partially hydrotreated hydrocarbon oil obtained at the stage (ii) in the second reactor at high temperature and pressure with hydrotreating catalyst in presence of pure hydrogen-containing gas with consumption of this hydrogen, at that at least 80% of hydrogen consumed at the stages (i) and (iii) are replenished by additional pure hydrogen-containing gas supplied to the second reactor; (iv) separation of the product produced at the stage (iii) in the second reactor into hydrotreated hydrocarbon oil and waste hydrogen-containing gas, at that hydrotreated hydrocarbon oil may be extracted as a product, and (v) transporting of at least a part of hydrogen-containing gas obtained at the stage (iv), which has temperature of at least 200°C to perform the stage (ii) while using this gas as stripping gas.

The present invention relates to a process for Hydrotreating hydrocarbon oils, which use at least the first and second reactors are placed in series.

Methods of Hydrotreating hydrocarbon oils are widely known. In addition, the literature describes the ways in which use two or more reactors.

Ways to reduce the number of compounds containing sulfur or nitrogen, and aromatic hydrocarbons are called, in General, ways Hydrotreating. These methods can be further divided into (a) methods, which mainly aims at saturating unsaturated compounds such as aromatic compounds and olefins, and in this case they are called methods, hydrogenation, and b) methods, which are aimed mainly at reducing the amount of sulfur-containing compounds and in most cases also compounds containing nitrogen, and in this case they are called methods of hydrodesulphuration. There are also ways aimed in particular at reducing the number of compounds containing nitrogen, which is removed only by a relatively small number of compounds containing nitrogen. They are called methods gidrogenizirovanii. The term "ways of hydrodesulphuration" as used hereinafter, refers to such ability�s,
aimed at the removal of sulfur-containing compounds and, optionally, a certain amount of nitrogen. The ways in which are isomerized linear paraffinic hydrocarbons to obtain branched alkanes are called methods of hydroisomerization or hydrodewaxing. These methods can be applied to middle distillates in order to reduce the temperature of solidification. Alternatively, this method can be applied to lubricating oils to improve the viscosity index.

Method Hydrotreating, which use two successive set of reactor described in patent document EP 611816 A. In the above document discloses a method of Hydrotreating, in which fresh hydrocarbon oil contacts in the first reactor with a Hydrotreating catalyst in the presence of hydrogen gas used. The effluent (effluent) thereafter contacting the partially divided into gidroabrazivnoy hydrocarbon oil and contaminated hydrogen-containing gas. The said separation is carried out in a Stripping column (Stripping column), using as the Stripping gas (boil-off gas) fresh pure hydrogen. Partially gidroabrazivnoy hydrocarbon oil contacts in the second reactor with a Hydrotreating catalyst in the presence of pure hydrogen gas. �the same time this stage of the method is divided into gidroabrazivnoy hydrocarbon oil and used hydrogen-containing gas,
thus gidroabrazivnoy hydrocarbon oil may be withdrawn as product, and the used hydrogen-containing gas is passed into the first reactor.

Method corresponding to the known analogue, has a drawback, which is that while you improve the efficiency of this method implements some integration in the stripper column is used hydrogen gas. Consequently, the net gas resulting mixed with contaminating impurities contained in the resulting stream from the first Hydrotreating reactor. Since the flow is obtained by mixing, contains significant amounts of hydrogen sulfide, before re-use in Hydrotreating reactors it is purified, for example by aminoacid. Obviously, in this case, the flow of pure hydrogen gas is excessively polluted and, accordingly, further purified, without its use in Hydrotreating reactions. In addition, the presence of cold pure hydrogen boil-off gas will contribute significantly to the partially cooled hydroblasting hydrocarbon oils, which increases the need for heat to achieve the desired process parameters in the second Hydrotreating reactor partially refined oil.

In document WO-A-200248285 disclosed method GI�of roopavathi using is included in the processing circuit of the intermediate otparku.
In known from the document the way Hydrotreating between the two zones is hydrotreated intermediate Stripping. The resulting stream from the second reactor is directed through a heat exchanger where it is cooled, in the separation zone. The separator in the separation zone separates the liquid product from the gases. The gaseous products from the separator is sent to the first reactor, where it is used as a Stripping gas. For this a certain amount of product gas may be directed into the supply line of the first reactor.

The disadvantage of the above method is that the cooled gas recirculation will result in significant cooling of the partially hydroblasting hydrocarbon oils in a Stripping column, thereby increasing the need for heat to achieve the desired parameters of the partially hydrotreated hydroblasting oil in the second reactor. An additional drawback is that the main supply of hydrogen is carried out in the first reactor. Fresh hydrogen is overly contaminated with impurities.

In patent document US 20060118466 As described Hydrotreating method comprising at least two stages of the reaction with intermediate fractionation. Stripping column operates using purified in a suitable�accordance with the terms of make-up hydrogen.
In addition, results from the second flow reactor was cooled and the gases separated at low temperature with the separator drum. In addition, in this case, hydrogen gas before using it again cool.

In patent document WO A described production method of the base oil. Recirculating hydrogen gas before reusing cleaned. Cold pure hydrogen gas will lead to a marked cooling of the partially hydroblasting hydrocarbon oil, thereby increasing requirements for supply of heat to achieve the desired process parameters hydrodewaxing oil in the second reactor. In addition, in accordance with the document US V hydrogen from the second reactor was cooled, and then to conduct separate recirculation phase separation. To the stripper, placed between the two reactors, serves hydrogen, essentially sulfur-free.

In patent document WO 2003080769 And the described method of hydrocracking to produce high-quality distillates from heavy gas oils. The said invention is directed to the use of hot stripper columns and separators disposed between the levels of the first and second reactors using a single circuit of hydrogen. The flow coming from the top of the second �of eector,
containing mainly hydrogen, is cooled in the heat exchanger and sent to a cold high pressure separator. Furthermore, in this known method, a hydrogen-containing gas before using it again cool. Another disadvantage of cold gas recirculation in the known method is that before he can be re-used in a Stripping column or in the reactor, it recompression.

The object of the present invention is further optimization of the method of the prior art.

In this regard, the present invention provides a method of Hydrotreating a hydrocarbon oil, which is used at least first and second reactors, wherein the method includes:

(i) contacting a hydrocarbon oil in the first reactor at elevated temperature and pressure with a Hydrotreating catalyst in the presence of hydrogen-containing gas, wherein hydrogen is consumed;

(ii) separation of the effluent obtained in stage (i), partially gidroabrazivnoy hydrocarbon oil and contaminated hydrogen-containing gas through the stripper column, in which the boil-off gas use hydrogen gas;

(iii) contacting the partially hydroblasting hydrocarbon oil obtained in stage (ii), in the second reactor PR� elevated temperature and pressure with a Hydrotreating catalyst in the presence of pure hydrogen gas,
with the consumption of hydrogen, and at least 80% of the hydrogen consumed in the stages (i) and (iii) compensate with additional clean hydrogen-containing gas fed into the second reactor;

(iv) separation of the product produced in stage (iii) in the second reactor, gidroabrazivnoy hydrocarbon oil and used hydrogen-containing gas, wherein gidroabrazivnoy hydrocarbon oil may be withdrawn as product and

(v) transportation, at least part of the used hydrogen-containing gas of step (iv) to carry out step (ii) for use as a Stripping gas.

Method according to the present invention efficiently uses in the stripper column all the gaseous components contained in the used hydrogen-containing gas. The proposed method also allows the use of gaseous hydrocarbons, which may be formed in the second Hydrotreating reactor, in the process of otparku. In addition, since the used hydrogen-containing gas is discharged directly from the second Hydrotreating reactor without any cooling, it can be used when the parameters required for Hydrotreating, including fever. Used hydrogen gas, which in this POV�high-temperature,
will further facilitate otparku and will improve the utilization therein of heat. Preferably used hydrogen-containing gas has a temperature of at least 200°C, more preferably at least 250°C., even more preferably at least 300°C and at most 400°C. the Pressure used hydrogen-containing gas is preferably at least 10 bar, more preferably at least 20 bar.

The maximum amount of pressure used hydrogen-containing gas is preferably 100 bar.

In accordance with a preferred embodiment in which hydrogen gas is gradually moving from the second stage reactor in the intermediate Stripping column and in the first stage reactor, the gas flow is used very effectively, thereby minimizing the required performance of the compressor. In addition, since the circuit with a hydrogen-containing gas is not cooled, there is no need to use lower pressure valve, and thereby minimizes the required pressure drop in the compressor.

Generally, it is advantageous to perform cleanup of hydrocarbon oils, the main volume of which, for example, more than 70 wt.%, acceptable more than 80 wt.% and preferably more than 90 wt.%, is in a liquid condition�and process parameters
available in the first reactor. Hydrocarbon oils that may be properly subjected to the hydrotreated in accordance with the present invention include kerosene fraction, the fraction of gas oil (gas oil) and lubricating oil. In particular, the present invention is very convenient and can be applied to gas oil fraction, since the restrictions on the environment for gas oils become more strict. Suitable gas oil may be one in which the major part of the hydrocarbons, for example at least 75 wt.% boils in the temperature range from 150 to 400°C. a Suitable lubricating oil contains at least 95 wt.% hydrocarbons, boiling in the range from 320 to 600°C.

The Hydrotreating process can be Hydrotreating process (in which the oil is changed slightly, it may be a hydrocracking process in which the average number of carbon atoms in the molecules of the oil decreases, this can be the process of hydrodemetallization in which the hydrocarbon is removed metal components; this may be hydrogenation, in which unsaturated hydrocarbons hydrogenizing and saturate; this can be a hydrodewaxing process in which molecules with straight chains are isomerized, or it can be a process for hydrogenation desulfurization in which from the feedstock �Dalat sulfur compounds.
It was found that the proposed method is in particular useful if the hydrocarbon feedstock contains sulfur compounds, and conditions of the Hydrotreating represent the conditions of hydrodesulphuration. The proposed method is advantageous in the processing of sulfur-containing feedstock, which contains the so-called bad recyclable sulfur compounds, i.e. compounds containing dibenzothiophen.

Parameters Hydrotreating, which can be implemented in the method in accordance with the present invention are not strictly necessary and may be modified in relation to the type of conversion, which is subjected to the hydrocarbon feedstock. Typically the options include Hydrotreating temperature in the range from 250 to 480°C, preferably from 320 to 400°C, a pressure in the range from 10 to 150 bar, preferably from 20 to 90 bar, and the average hourly feed rate of the raw material in the range from 0.1 to 10 h-1preferably from 0.4 to 4 h"1. The specialist may choose these parameters in accordance with the type of substrate and the desired form of Hydrotreating.

The catalyst used in the present invention, can also be selected in accordance with the desired conversion. Suitable catalysts include, at a minimum, the metals of groups VB, VIB and/or VIII of the Periodic table e�cops on a suitable carrier.
Examples of suitable metals include cobalt, Nickel, molybdenum and tungsten, but can also be used noble metals such as palladium and platinum. In particular, if the hydrocarbon oil contains sulfur, the catalyst, respectively, containing a carrier and at least one metal from group VIB and group VIII. Despite the fact that these metals may be in the form of their oxides, it is preferable to use metals as sulphides. Since the catalyst can usually be obtained in the form of oxide, these catalysts can then be processed by pre-sulfatirovnie, which can be accomplished outside of the conversion process, but preferably is held in place, in particular, in conditions that are similar to effective conversion.

Metals suitable way to combine media. The media may be non-crystalline refractory oxide, such as silicon oxide, aluminum oxide or system "silicon oxide - aluminum oxide". Can also be used and other oxides such as zirconium oxide, titanium oxide or Germany. For hydrodewaxing processes can be used crystalline aluminosilicates, such as betazole, ZSM-5, mordenite, ferrierite, ZSM - 11, ZSM-12, ZSM-23 and other zeolites with medium porosity. If conditions for hydrocast�and lead to hydrocracking,
the catalyst may preferably represent another zeolite. Suitable zeolites are zeolites of type faujasite, such as zeolite X or Y, in particular, an ultra-stable zeolite Y. it is also Possible the use of zeolites with large pores. These zeolites are usually combined with an amorphous binder, such as alumina. Metals suitable manner is combined with the catalyst by impregnating, soaking, joint crushing, grinding or additionally, in the case of zeolites by ion exchange. It is obvious that the specialist knows what catalysts are appropriate and how such catalysts can be prepared.

The term "clean hydrogen-containing gas" here refers to a gas which contains less than 0.1 vol.% hydrogen sulfide based on the total gas volume, preferably less than 0.01 vol.%, more preferably less than 20 ppmv (ppm per unit volume) and most preferably less than 5 ppmv of hydrogen sulfide. Examples of pure hydrogen-containing gas can include fresh make-up hydrogen is obtained, for example, in the steam reforming process, or contaminated by impurities hydrogen-containing gas is subjected to processing for the purpose of cleaning, for example, using amine. Such contaminated gas can be obtained by carrying out the proposed FPIC�BA,
but, in addition, may be subject to cleaning and subsequently used in the proposed method the contaminated hydrogen gas from other sources or processes. The content of hydrogen in pure hydrogen-containing gas is preferably at least 95 vol.%, more preferably at least 97%, based on the total volume of pure hydrogen gas.

In the first embodiment of the hydrogen-containing gas, which is used in stage (i) in the first reactor, is pure hydrogen gas. As a result, the amount of gas required for filing in the first reactor can be minimized. This gas can be appropriately obtained in the purification of contaminated hydrogen-containing gas, such contaminated gas that is available for use in the method. Hydrogen gas, which is used in stage (iii) in the second reactor, is a pure hydrogen gas needed to fill the hydrogen consumed in the first and second reactors, possibly augmented clean purified gas.

According to another preferred embodiment of the effluent from the first reactor before it can be used in the stripper column is transported in the gas-liquid separator. Gaseous phase in this exposure�hydrology and hydrogeology stream usually contains a large amount of impurities,
such as hydrogen sulfide and ammonia, for example from 0.5 to 5.0 vol.%, based on the total volume of the gas phase. Accordingly, this phase is withdrawn as contaminated hydrogen-containing gas in the gas-liquid separator, and preferably it may be provided in the cleaning section, such as a scrubber that uses aminoacid. The liquid phase containing partially gidroabrazivnoy hydrocarbon oil, is withdrawn from the gas-liquid separator and fed to the stripper column. Stripping column operates with the used hydrogen-containing gas coming from the second reactor. In the first reactor as a hydrogen-containing gas is preferably directed to the combination of the used hydrogen-containing gas and boil-off gas. It is clear that in this embodiment for the separation of stage (ii) in addition to a Stripping column using gas-liquid separator. In this gas-liquid separator remove most of the impurities and components containing lighter hydrocarbons. The remaining impurities, which served in the first reactor, are present in small numbers and do not affect the process in the first Hydrotreating reactor.

The first reactor in the preferred embodiment operates with the use of hydrogen-containing gas, which contains a number of impurities.

At this�stage Hydrotreating hydrogen is consumed.
In General, the consumption of hydrogen for Hydrotreating stages for the method is not standardized and depends on the type of the treated hydrocarbon oils. In General, the consumption of hydrogen in each of the reactors in the conditions of the Hydrotreating is in the range from 0.1 to 2.5 wt.%, based on the weight of hydrocarbon oil for the first reactor and the mass of partially hydroblasting hydrocarbon oils for the second reactor. The hydrogen used in the first and second reactors, duly completed, at least 80% by adding a second reactor clean hydrogen-containing gas. In this way, the amount of gas that becomes contaminated with significant quantities of impurities in the first reactor is minimized. Further minimization can be appropriately achieved by additions of at least 90%, more preferably essentially 100% of the hydrogen used in the first and second reactors, clean hydrogen-containing gas into the second reactor.

Flow exiting the first reactor contains partially gidroabrazivnoy hydrocarbon oil. In the second stage is partially gidroabrazivnoy hydrocarbon oil is separated from the contaminated hydrogen-containing gas. In a preferred embodiment of the subject to the treatment of hydrocarbon oil is a gas oil, to�which usually contains sulfur compounds.
In the first reactor, these sulfur compounds are converted into hydrogen sulfide, which pollutes hydrogen gas. In accordance with the method according to the present invention the contaminated hydrogen gas is separated from the partially hydroblasting hydrocarbon oils in the stripper column. In the process of otparku as boil-off gas is used used hydrogen-containing gas that is offset from stage (iv). The thus obtained contaminated hydrogen-containing gas is appropriately cleaned and re-used as pure hydrogen gas at the stage (iii) and optionally, in step (i).

The cleanup of contaminated hydrogen-containing gases, in particular if they are contaminated with hydrogen sulfide and other sulfur compounds such as sulfur dioxide or seraikis carbon are well known. The appropriate method of removal of these contaminants briefly disclosed in the patent document EP 611816 and represents an amine treatment.

In the process of purging contaminated hydrogen-containing gas is properly in contact with an aqueous solution of amine. Specified the aqueous solution contains one or more compounds. Suitable compounds are primary, secondary and tertiary amines. Preferably amines contain at least one oxyalkylene group. Alkyl �Rupp in such a group contains,
in General, from 1 to 4 carbon atoms. In the case of secondary and tertiary amines of aminosidine preferably contain one or more alkyl and hydroxyalkyl groups, each of which preferably contains from 1 to 4 atoms. Suitable examples of the compounds include monoethanolamine, monoethanolamine, monomethylethanolamine, diethylaminoethylamine, diethanolamine, triethanolamine, diisopropanolamine, diethylenglycol, diethanolamine, and mixtures thereof. Other suitable compounds are N,N'-di(hydroxyalkyl)piperazine, N, N, N',N'- tetrakis(hydroxyalkyl)-1,6-hexanediamine in which the alkyl group can contain from 1 to 4 carbon atoms.

The aqueous solution may also contain physical solvents. Suitable physical solvents include tetramethylsilane (sulfolane), and derivatives, amides of aliphatic carboxylic acids, N-alkylpyridine, in particular N-methylpyrrolidine, N-alkylpiperidines, in particular N-methylpiperidin, methanol, ethanol, ethylene glycol, the bag. anglicani, mono - or di-(C1-C4)-alkylamine of ethylene glycol or of polyethylene glycols having, in General, a molecular weight of from 50 to 800, and mixtures thereof.

The concentration of aminosidine in aqueous solution can vary within wide limits. The specialist will be able to determine suitable concentrations without excessive effort. Before�occhialino the aqueous solution contains,
at least 15 wt.% water, aminosidine from 10 to 65 wt.%, preferably from 30 to 55 wt.%, and the physical solvent is 0 to 40 wt.%, where all the interest is determined based on the weight of water, aminosidine and physical solvent.

The conditions in which the contaminated hydrogen-containing gas is treated with an amine, include temperature in the range of 0 to 150°C, preferably from 10 to 60°C and a pressure of 10 to 150 bar, preferably from 35 to 120 bar.

A Stripping gas in a Stripping column contains the used hydrogen-containing gas. Since the boil-off gas becomes available for use after Hydrotreating reaction stage (iii), it can be used at elevated temperatures. Due to the fact that the increased temperature improves the efficiency of otparku compared with the efficiency of otparku cold gas and prevents the cooling in the process of otparku, it is obvious that the proposed method provides an additional advantage, which is to increase the efficiency of the process of otparku. Used hydrogen-containing gas that is used as a Stripping gas in step (ii) preferably has a temperature of from 250 to 480°C, preferably from 320 to 400°C.

Some part or all partially gidroabrazivnoy hydrocarbon oil is subjected to further hydrotreated in St�stage (iii).
As noted above, the proposed method is particularly advantageous in the case where the treated hydrocarbon oil is a gas oil. Therefore, particularly preferably as a catalyst for Hydrotreating stage (i) was used the catalyst hydrodesulphuration, and at stage (iii) as a catalyst for Hydrotreating - hydrodewaxing catalyst or catalyst hydrodearomatization. In such cases, the catalyst hydrodesulphuration, respectively, represents selected at the discretion sulpicianus the catalyst containing one or more metals from groups V, VI and VIII of the Periodic table of elements, on a solid support. As noted earlier, the solid support can be selected from among those listed above refractory oxides. The catalyst hydrodesulphuration, in particular, may contain one or more metals, including Nickel and cobalt, and one or more metals, including molybdenum and tungsten. The catalyst may preferably be, as noted above, solifidian.

The hydrodewaxing catalyst comprises as catalytically active metal is one or more noble metals selected from the group VIIII of the Periodic table of elements, on a solid support. Preferably the noble metal is selected from groups�,
consisting of platinum, palladium, iridium and ruthenium.

The media mostly contains zeolite (from among the above-mentioned zeolites) in combination with a binder material. Suitable binder materials include aluminum oxide, silicon oxide and the composition of silicon oxide and aluminum oxide. However, it can also be used and other refractory oxides.

If the stage Hydrotreating is carried out in stage (iii), using the hydrodewaxing catalyst or catalyst hydrodearomatization, the process parameters, which can be applied in the method corresponding to the present invention, typically include a temperature in the range from 200 to 400°C, preferably from 250 to 350°C, a pressure of from 10 to 150 bar, preferably from 20 to 90 bar, and the average hourly feed rate of the raw material in the range from 0.1 to 10 h-1preferably from 0.4 to 4 h-1. The expert can find the most suitable options according to the type of raw material.

At stage (iv) withdrawing a product stream in the second Hydrotreating reactor is withdrawn and divided into gidroabrazivnoy hydrocarbon oil and used hydrogen gas. According to stage (v) of the proposed method, at least part of the used hydrogen-containing gas is transported to the stage (ii) for use as a Stripping gas. PR�doctitle,
at least 90 vol.% used hydrogen-containing gas is transported to the stage (ii), more preferably at least 95 vol.%, and most preferably the entire volume of the used hydrogen-containing gas is transported to the stage (ii).

The separation stage (iv) can be produced by any suitable means. One suitable way involves the use of means of separation inside the second reactor comprising a downward sloping plate between the lower end of which and the wall of the reactor vessel has an opening. Preferably at the lower end of the plate there is a passing down curled edge. Such a plate is described in patent document EP 611861 A. alternatively, can be used one or more dividing plates placed in the lower part of the housing of the second reactor. In another embodiment the separation of the effluent after Hydrotreating in the second reactor is carried out in a separate gas-liquid separator, alternatively, with additional heat integration. Specified effluent from the reactor stream, before or after separation, may be appropriately used for heat exchange with partially hydroallantois hydrocarbon oil emerging from the stripper column. The advantage of this solution is that leaving�th of the flow reactor is cooled,
while partially gidroabrazivnoy hydrocarbon oil may be heated to the desired temperature Hydrotreating without using an external source of heat, such as additional heating furnace. Obviously, this decision creates a significant advantage from the standpoint of economy and efficiency of heat utilization.

Fig.1 is a schematic flow diagram corresponding to one embodiment of the present invention.

Fig.2 is an alternative embodiment of the method according to the present invention.

Fig.1 shows a pipe 1 through which the hydrocarbon oil is transported through the heat exchanger 2 and which is added to pure hydrogen gas via conduit 3. The mixture of hydrogen gas and the hydrocarbon fuel is transported through the furnace 4, and the heated mixture through a pipeline 5 is directed into the first reactor 6 Hydrotreating. In the first reactor 6 Hydrotreating placed three layers of catalyst. However, the number of catalyst layers is not strictly defined and can be changed in order to meet the required conditions of Hydrotreating. In the gap between two subsequent layers add pure hydrogen gas through pipelines 3C and 3d, respectively. In principle, the flow in the first and second reactors can�t to flow up or down.
It is preferable to transport the hydrogen-containing gases and hydrocarbon oil or partially gidroabrazivnoy hydrocarbon oil through the reactor in one direction, in the parallel flow mode and lowering of the flow (flow from top to bottom). It is possible to reliably regulate the gas flow rate and liquid flow rate. It is also easier to control the reaction temperature. The resulting product stream from the first reactor is withdrawn through line 7. This stream is also passed through a heat exchanger 2 for preheating the hydrocarbon oils to be hydrotreated, and then sent to the stripper 8. In the lower part of the stripper column 8 through line 10 as boil-off gas serves the used hydrogen-containing gas and the gaseous components contained in the flowing out of the reactor stream is transported via conduit 7, is removed with a Stripping gas in the form of contaminated hydrogen-containing gas through a pipeline 9. Contaminated hydrogen-containing gas is treated in an absorption column 18, irrigated amine, and clean, and pure hydrogen gas removed via conduit 3. Pipeline 3 branches at the branch 3A of the pipeline that feeds into the hydrocarbon oil, hydrogen gas, and the branch 3b conduit which, in turn, is divided into Truboprovod and 3d for supplying the first reactor 6 additional hydrogen for the purpose of regulating the temperature in the reactor.
Should be taken into consideration that although the absorption of the amine shown in Fig.1 implemented with a single absorption column 18, the complex of aminoacid includes columns of absorption and desorption, and optionally, one or more compressors. In addition, pure hydrogen gas flowing in the conduit 3 may be subjected to heat exchange with one or more process streams, for example, contaminated hydrogen-containing gas flowing through the conduit 9, and/or the flow exiting the first reactor and transported by pipeline 7.

Stripped, partially gidroabrazivnoy hydrocarbon oil is withdrawn from the stripper column 8 via line 11. Optionally, partially gidroabrazivnoy hydrocarbon oil is transported via conduit 11, is passed through the furnace 12, and the heated oil through the pipeline 13 is directed to the second reactor 14. Pure hydrogen gas (in this particular case, the fresh make-up hydrogen) is fed to the reactor 14 through conduit 16. In accordance with the present invention, at least 80% of hydrogen to be added in connection with its use in reactors 6 and 14, is added to the reactor 14. Specialist in the art it is clear that, if desired, some portion of fresh feed�tion of hydrogen,
i.e. up to 20% of the used hydrogen may be replaced by a flow of hydrogen gas from the pipeline 3. In the upper part of the reactor 14 is placed a layer of catalyst, while in the lower part of the separation plate 15, which allows the reaction product from the catalyst layer to flow into the lower portion of the reactor, but prevents the passage of the gaseous component in the opposite direction. The reaction product is separated into gidroabrazivnoy hydrocarbon oil and used hydrogen gas. The gaseous components, namely, the used hydrogen-containing gas is withdrawn from reactor 14 through conduit 10, which transports specified hydrogen gas to the stripper 8. Liquid gidroabrazivnoy hydrocarbon oil is removed through line 17. Products transported via conduit 17 may be separated into fractions by any known method.

Fig.2 shows a schematic process flow diagram according to an alternative embodiment of the invention. The diagram shows the conduit 21 through which the hydrocarbon oil is transported through the heat exchanger 22 and in which by means of conduit 23 is added hydrogen gas. Hydrogen gas enters the conduit 23 of the stripper column 31 and contains hydrogen, which tries�was conducted in contact with a Hydrotreating catalyst in the reactor 40 and the stripper column 31.
Mixed hydrogen gas and the hydrocarbon oil is heated in the furnace 24 and through the conduit 25 is transported in the first reactor 26 Hydrotreating. Withdrawing a product stream from the reactor 26 is directed through the heat exchanger 22, is used for pre-heating of hydrocarbon oils, in the gas-liquid separator 28. The liquid product containing partially gidroabrazivnoy hydrocarbon oil, is transported to the stripper column 31 through line 30, into a gaseous product containing a substantial portion of the impurities, namely, impurities that were in the hydrogen-containing gas, plus impurities formed in the reaction process in the reactor 26 is withdrawn from the gas-liquid separator 28 through conduit 29. Partially gidroabrazivnoy hydrocarbon oil is subjected to a Stripping column 31 Stripping using a hydrogen-containing gas that is formed in the second reactor 40 Hydrotreating.

Boil-off gas together with any volatile component, which is extracted from the partially hydroblasting hydrocarbon oil, is discharged through line 23. The gas passing through conduit 23 will contain hydrogen, a certain amount of light gaseous hydrocarbons and only a small proportion of impurities containing heteroatoms, such as hydrogen sulfide and �MIAC.
This gas is used as a hydrogen-containing gas to the first reactor. Since most of these impurities was separated in the gas-liquid separator 28 and allotted through conduit 29, the gas passing through conduit 23 may be appropriately used as a hydrogen-containing gas for Hydrotreating reactor 26. If necessary, partially gidroabrazivnoy hydrocarbon oil obtained in the stripper column 31 can be directed therefrom through conduit 33 into the furnace 34 where it is heated to the desired temperature for the second reactor.

With proper heat integration between the effluent stream from the second reactor and partially hydroallantois hydrocarbon oil, which is used as feedstock for the second reactor, furnace 34 may be eliminated, allowing the second reactor to operate in the so-called "auto" mode. The heated hydrocarbon oil is directed through the conduit 35 into the second reactor 40 where it is mixed with clean hydrogen-containing gas supplied through conduit 36A. Between successive layers of the catalyst can be fed additional hydrogen through conduit 36A and 36, respectively. By a conduit 37 the reaction product from the reactor 40 is transported in a hot gas-liquid separator 41, in which hydraulic�treated hydrocarbon oil is separated from the used hydrogen-containing gas.
Used hydrogen-containing gas is removed via conduit 32 and transported to the stripper 31. Gidroabrazivnoy hydrocarbon oil is discharged through the conduit 42 and is taken in the quality of the product. The product, identified through a conduit 42, may be subjected to fractionation to obtain the desired specific hydrocarbon product.

Contaminated hydrogen-containing gas through pipeline 29 is directed into the complex aminoacid shown in Fig.2 column 39. In column 39 of contaminated hydrogen-containing gas impurities and the result is pure hydrogen gas, which is removed via conduit 36. To clean hydrogen-containing gas in the conduit 36 through line 38 add fresh make-up hydrogen, in this case in the amount of complement to 100% hydrogen, which is to be used in the process. The conduit 36 may be branched at the branch 36A, 36b and 36C for supplying hydrogen to the reactor 40 at various points of entry.

Should be taken into account, which is considered not shown, auxiliary equipment, which are usually used, such as valves, pumps, compressors, expansion devices, instrumentation, etc., the Specialist will be clear where you want to install accessories such�e equipment.

1. A method of Hydrotreating a hydrocarbon oil using at least first and second reactors, wherein the method includes:(i) contacting a hydrocarbon oil in the first reactor at elevated temperature and pressure with a Hydrotreating catalyst in the presence of hydrogen-containing gas, in which the consumption of hydrogen;(ii) separation of the effluent obtained in stage (i), partially gidroabrazivnoy hydrocarbon oil and contaminated hydrogen-containing gas through the stripper column, in which the boil-off gas is used used hydrogen gas;(iii) contacting the partially hydroblasting hydrocarbon oil obtained in stage (ii), in the second reactor at elevated temperature and pressure with a Hydrotreating catalyst in the presence of pure hydrogen gas, with the consumption of hydrogen, and at least 80% of the hydrogen consumed in the stages (i) and (iii) compensate with additional clean hydrogen-containing gas fed into the second reactor;(iv) separation of the product produced in stage (iii) in the second reactor, gidroabrazivnoy hydrocarbon oil and used hydrogen-containing gas, wherein gidroabrazivnoy hydrocarbon oil can be extracted as� product,
and(v) transportation, at least part of the used hydrogen-containing gas of step (iv), which has a temperature of at least 200°C in the process (ii) for use as a Stripping gas.

2. A method according to claim 1, wherein the used hydrogen-containing gas has a temperature of at least 250°C., more preferably at least 300°C and at most 400°C.

3. A method according to claim 1 or 2, which used hydrogen-containing gas has a pressure of at least 10 bar, preferably at least 20 bar.

4. A method according to claim 1 or 2, in which the subject hydrotreated hydrocarbon oil is a gas oil which contains at least 75 wt.% hydrocarbons boiling in the temperature range from 150 to 400°C.

5. A method according to claim 1 or 2, in which the subject hydrotreated hydrocarbon oil is a lubricating oil, which contains at least 95 wt.% hydrocarbons boiling in the temperature range from 320 to 600°C.

6. A method according to claim 1 or 2, wherein the parameters include Hydrotreating temperature in the range from 250 to 480°C, a pressure in the range from 10 to 150 bar and the average hourly feed rate of the raw material in the range from 0.1 to 10 h-1.

7. A method according to claim 1 or 2, in which pure hydrogen gas contains less than 0.1. % of hydrogen sulfide.

8. �appliance according to claim 1 or 2,
in which coming from the first reactor stream is directed into the gas-liquid separator before it is used in the stripper column.

9. A method according to claim 1 or 2, wherein the contaminated hydrogen-containing gas of step (ii), purified and reused in the process (iii) and, optionally, in step (i).

10. A method according to claim 9, in which the contaminated hydrogen gas is purified by aminoacid.

11. A method according to claim 1 or 2, wherein at least 90%, preferably essentially 100% of the hydrogen used in the stages (i) and (iii) compensate at the expense of additional clean hydrogen-containing gas fed into the second reactor.

12. A method according to claim 1 or claim 2, in which used hydrogen gas, which is used as a Stripping gas in step (ii), has a temperature in the range from 250 to 480°C.

13. A method according to claim 1 or 2, wherein the Hydrotreating catalyst of stage (i) is a catalyst hydrodesulphuration, and the Hydrotreating catalyst in stage (iii) is a hydrodewaxing catalyst.

14. A method according to claim 13, wherein said catalyst hydrodesulphuration contains one or more metals of groups VB, VIB and VIII of the Periodic table of elements on a solid support.

15. A method according to claim 14, wherein said catalyst hydrodesulphuration contains one or more metal� from cobalt and Nickel, and one or more of the metals molybdenum and tungsten.

16. A method according to claim 13, wherein the hydrodewaxing catalyst used in stage (iii) comprises as catalytically active metal is one or more noble metals from group VIII of the Periodic table of elements on a solid support

17. A method according to claim 16, in which the noble metals selected from the group consisting of platinum, palladium, iridium and ruthenium.

SUBSTANCE: proposed process comprises compression of boost hydrogen in first compressor to get first flow of compressed boost hydrogen. First flow of compressed boost hydrogen is compressed in second compressor to get second flow of compressed boost hydrogen. Said second flow of compressed boost hydrogen is separated as second flow of compressed boost hydrogen for hydraulic treatment. First flow of hydrocarbons is processed over first flow for hydraulic processing including second flow of compressed boost hydrogen and first hydraulic processing catalyst to get first effluent flow of hydroprocessing products. Second flow of hydrocarbons is processed over second flow for hydraulic processing including first flow of compressed boost hydrogen and first hydraulic processing catalyst to get second effluent flow of hydroprocessing products. Said second effluent flow of hydroprocessing products is separated to get vaporous second effluent flow of hydroprocessing products. Said vaporous second flow is added to said boost hydrogen flow upstream of said first compressor.

SUBSTANCE: invention relates to method of diesel fuel production. Particularly, it pertains to compression of makeup hydrogen flow in compressor to bleed hydrogen flow from said compressed makeup hydrogen flow. Hydrocarbons flow is subjected to hydro cracking in the presence of hydrogen flow and catalyst to get outlet hydro cracking products flow to be separated in liquid flow and vapour flow to be compressed to get hydrogen compressed flow. Liquid outlet flow is fractionated to obtain diesel fuel flow. Hydrogen flow is bled for hydraulic cleaning from said compressed hydrogen flow for hydraulic cleaning of diesel fuel flow in the presence of hydrogen flow and catalyst to get outlet hydro cracking products flow. Invention covers also the diesel fuel production plant.

SUBSTANCE: invention is related to hydrocracking processes, under conditions of which large proportion of heavy hydrocarbon stock e.g. Vacuum Gas Oil (VGO) turns to hydrocarbons with lower molecular mass and lower boiling temperature. The invention relates to the method of production of base oil, involving: a) hydrocracking of heavy hydrocarbon stock with hydrocracking catalyst containing the preset amount less than 15 wt % of beta-zeolite with flow coming out of a hydrocracking plant containing at least 40 wt % of hydrocarbons boiling at temperature of 382°C (720°F), and b) separation from flow coming out of a hydrocracking plant of unconverted oil with pour point not above 18°C (65°F) in form of high-boiling fraction containing base oil.

SUBSTANCE: invention is related to a combined method of conversion of oil-derived hydrocarbon fractions into high-quality hydrocarbon mixtures as fuel, which includes catalytic cracking of hydrocarbon fraction in catalyst fluidised bed with catalyst containing ERS-10 zeolite, where the specified catalyst contains at least two components, where the specified components represent: (a) a component containing one or more catalytic cracking catalysts in fluidised, and (b) a component containing ERS-10 zeolite for obtaining Light Cycle Gas Oil (LCGO), hydrotreatment of light cycle gas oil, interaction of hydrotreated light cycle gas oil obtained at the previous stage of hydrotreatment in presence of hydrogen with catalytic system. The invention also touches the method of catalytic cracking and a stage of catalytic cracking in fluidised bed.

SUBSTANCE: invention relates to the hydroconversion method for raw hydrocarbons in the mix with the circulating part of the hydroconversion vacuum residue by a high-aromatic modifier, dispersion of a catalyst precursor and hydrogen-containing gas which is supplied in the amount of maximum 800 nm3 per 1 m3 of raw material in terms of hydrogen and of minimum the value of chemical hydrogen demand. The above is carried out in a reactor with an internal circular baffle plate which adjoins the reactor top in a pressure tight way and forms axial and circular cavities, and with separation space at the top of the circular cavity. Hydroconversion gas is removed from the separation space, liquid hydroconversion product is removed from the top of the axial cavity, circulating reaction mass is removed from the bottom of the reactor's circular cavity, cooled and delivered for mixing with heated raw liquid-vapour mixture, the temperature of the liquid hydroconversion product is kept close to the upper limit of the hydroconversion temperature range, the temperature of the heated raw mixture and the temperature of the circulating reaction mass are kept close to the lower limit of the hydroconversion temperature range. Hydroconversion products are separated and rectified to isolate light fractions, heavy gas oil and vacuum residue, part of the latter is recirculated, and the balance part is recovered to produce regenerated catalyst precursor.

EFFECT: reduction of power inputs and metal consumption of equipment along with the provision for high yield of light fractions.

SUBSTANCE: invention relates to production of fuel for jet engines from kerosene stock. Proposed method comprises hydrofining of kerosene stock with freezing point interval of 163-302°C (325-575°F) over hydrofining catalyst under conditions of hydrofining. This allows getting hydrofined kerosene stock. Besides, it includes dewaxing of, in fact, all hydrofined kerosene stock over catalyst including 1-D molecular sieve with ten rings under conditions of dewaxing to get water-dewaxed kerosene stock. Also, it includes fractionating of water-dewaxed kerosene stock to get fuel for jet engines.

SUBSTANCE: initial hydrocarbon raw material is initially separated and first part of initial raw material is introduced into first zone of dehydration reaction, which functions without oxidation re-heating, and obtained as a result output flow is introduced into second zone of dehydration reaction, which functions without oxidation re-heating. Obtained as a result output flow from second zone of dehydration reaction, together with second part of initial raw material is introduced into third zone of dehydration reaction, which functions with oxidation re-heating.

SUBSTANCE: invention is referred to method of production of high-octane petrol and includes fractionation of hydrotreated naphtha into light and heave fractions; light naphtha isomerisation and heavy naphtha reforming in presence of platinum-containing catalyst with delivery of excessive hydrogen from reforming to isomerisation. Isomerisation is carried out with sulfate-zirconia catalyst with subsequent separation of isomerisate into three fractions: low-boiling fraction, medium fraction containing n-hexane and methylpenthanes and high-boiling fraction; medium fraction is recirculated to isomerisation raw material. By rectification from reformate light and heavy reforming fractions are obtained; heavy fraction is mixed with low- and high-boiling fractions of isomerisate with production of the target product while light fraction of reforming boiling away up to 85-95°C is subjected to hydroisomerisation at 250-300°C in presence of platinum-containing catalyst and obtained hydroisomerisate is delivered to be mixed with isomerisate.

EFFECT: reduction of benzole and aromatic hydrocarbons content in compliance with requirements to modern types of petrol with preservation of integration for reforming and isomerisation processes.

SUBSTANCE: invention relates to a method for hydrocracking a hydrocarbon stream involving the following operations: providing hydrocarbon starting material (12); feeding the hydrocarbon starting material (12) into a hydrofining zone (14) to obtain an output stream (30) of the hydrofining zone; feeding the output stream (30) of the hydrofining zone into a separation zone (16) in order to separate one or more streams of hydrocarbons with a lower boiling point (34, 58, 62, 66) from a stream of liquid hydrocarbons with a higher boiling point (68); inlet of at least a portion of the stream of liquid hydrocarbons with a higher boiling point as material (68) for hydrotreatment without using a considerable amount of hydrocarbons coming from the hydrotreatment zone with an essentially continuous liquid phase; adding hydrogen (70) to the material (68) for hydrotreatment in an amount which is sufficient to maintain essentially liquid-phase conditions; feeding the material (68), mixed with hydrogen, for hydrotreatment into the hydrocracking zone (24) with an essentially continuous liquid phase; and carrying out a reaction for hydrocracking the material (68) for hydrotreatment in the hydrocracking zone (24) with an essentially continuous liquid phase with a hyrocracking catalyst in hydrocracking conditions to obtain an output stream (72) of the hydrocracking zone having a lower boiling point compared to the stream (68) of liquid hydrocarbons with a higher boiling point. The invention also relates to another method for hydrocracking a hydrocarbon stream.

SUBSTANCE: method is described to produce hydrocarbon fractions, which may be used as diesel fuel or as components of diesel fuel, based on a mixture of biological origin, containing ethers of fatty acids, possibly, with a certain amount of free fatty acids, which includes the following stages: 1) hydrodesoxygenation of a mixture of organic origin; 2) hydroisomerisation of a mixture produced at the stage (1), after possible treatment for cleaning; besides, the specified stage of hydroisomerisation is carried out in presence of a catalytic system, which contains the following: a) a carrier of acid nature, including a fully amorphous micro-mesoporous silicon-aluminium oxide, having a mole ratio SiO2/Al2O3 in the range from 30 to 500, the surface area of more than 500 m2/g, volume of pores in the range from 0.3 to 1.3 ml/g, the average diameter of pores below 40 Ǻ, b) a metal component containing one or more metals of group VIII, possibly mixed with one or more metals of the group VIII.

EFFECT: production of a hydrocarbon fraction, which may be applied as diesel fuel or as a component of diesel fuel.

SUBSTANCE: claimed method includes hydrofining of by-product-coke resin with subsequent hydrodealkylation. In hydrofining step hydrogen donators such as naphthalene, anthracene, and phenanthrene hydro- or alkyl-derivatives, containing in coal-far resin, are obtained. Dealkylation is carried out using the said hydrogen donators. Quantitative content of hydrogen donators is equal the same of benzene, naphthalene, alkyl-derivatives, and other hydrodealkylated compounds (15-30 wt.% as calculated to raw material). Hydrofining is carried out under hydrogen pressure of 2-5 MPa, at 280-4000C, feed space velocity of 0.5-2 h-1, in hydrogen/feed ratio of 500-1000 l/kg in flowing system.

SUBSTANCE: light cracking naphta is processed to convert mercaptans into sulphides and saturation of dienes and then later subjected to destructive hydrodesulfurisation (HDS) to convert organic sulphur compounds into hydrogen sulphide. Recombinant mercaptans, formed from reaction of hydrogen sulphide with olefins at the HDS output, usually heavier than the cracking naphta, are fractionated in a mixture with the heavy cracking naphta. The invention pertains to the method of extracting organic sulphur compounds, including mercaptans, from light cracking naphta (LCN), including the fractionated mixture, consisting of hydro-treated LCN, containing the initial quantity of organic sulphur compounds, including mercaptans, and heavy cracking naphta (HCN), with volume ratio of HCN:LCN ranging from 4:1 to 1:4, in the fractionating zone in corresponding temperature and pressure conditions for removal of fractions of still residues, containing the stated HCN and part of the organic compounds of sulphur from LCN, and light ends, containing LCN and organic compounds of sulphur in quantity less than that yielded from the fractionating zone.

SUBSTANCE: in method of obtaining distillates and residues for oil bases from hydrocarbon charge: a) charge is subjected to cracking in presence of hydrogen and hydrocracking catalyst, at least, in one reactor with boiling layer with possibility of conversion, at least, of 10 wt % of charge fraction, boiling at temperature over 370°C, into compounds with boiling point lower than 370°C; b) at least, part of effluent, obtained at stage a), is fractioned for isolation of, at least, first residue, at least, 85 wt % of whose compounds start boiling at temperature 320°C, said first residue containing aromatic compounds; c) at least, part of aromatic compounds from, at least, part of first residue is removed in order to obtain effluent with low content of aromatic compounds, content of aromatic compounds being less than 30 wt %; d) at least, part of effluent, obtained at stage c) is fractioned in order to isolate second residue for oil bases with output , at least, 15 wt % with respect to charge.

EFFECT: possibility to combine production of high-quality lubricating oils with performing preliminary cracking in reactor with boiling layer.

SUBSTANCE: present invention is related to the field of oil processing, more precisely, to method for production of diesel fuel intended for use under conditions of low temperatures in the environment. Invention is related to method for production of diesel fuel, including hydrodewaxing of medium-boiling diesel fraction, which boils away in the range of 240-340°C on zeolite-containing catalyst, mixing of hydrodewaxed diesel fraction with kerosene fraction in the following ratio, wt %: 40-80:20-60 and hydraulic treatment of mixture on aluminium-cobalt-molybdenum or aluminium-nickel-molybdenum catalyst at increased temperature and pressure to produce finished product.

EFFECT: production of diesel fuel for cold and arctic climate, with content of sulfur level that complies with according European standards and requirements of GOST R 52368-2005.

SUBSTANCE: invention relates to the method of hydroconversion combined with desulfurization in a reaction zone of sulphur-containing heavy hydrocarbon charge with hydrogen and a solid catalytic phase added, while said solid catalytic phase is prepared of a catalytic precursor wherein the conversion products supplied from the reaction zone are separated in an internal or external gas-liquid separator, and the catalytic precursor is injected in a liquid portion of conversion products recycled in the reaction zone; the portion saturated with dissolved hydrogen sulphide and containing pyrobitumens and/or resins and the catalytic precursor is injected in the specified liquid products with temperature within TS+/-10°C where Ts is outlet temperature of the specified liquid products from the reaction zone, and total pressure is within Ps+/-10 bar where Ps is outlet pressure of the specified liquid products from the reaction zone; said temperature makes 380°C to 500°C, and the prepared mixture reacts in the reaction zone. The invention also concerns an apparatus for implementation of this method.

SUBSTANCE: invention refers to oil refining industry, namely to method of obtaining high-octane motor petrol. Invention deals with method for obtaining motor petrol, which involves separation of petrol distillate of catalytic cracking into light and heavy fractions, hydroforming of heavy fraction mixed with straight-run diesel fraction, further additional hydroforming of extracted hydrotreated petrol fraction mixed with straight-run petrol fraction. Extracted hydrotreated petrol fraction is separated into two parts, one of which is subject to additional hydroforming mixed with straight-run petrol fraction; after that, it is directed to catalytic reforming, and the other part is mixed with light fraction of petrol distillate of catalytic cracking and catalysate of catalytic reforming in the following ratio, % wt: 20:40:40-10:30:60 respectively so that commercial motor petrol is obtained.

EFFECT: compliance of base components of high-octane motor petrols as to quality with European standards.

SUBSTANCE: invention relates to a fixed layer hydrogen treatment system, as well as methods of improving the existing fixed layer hydrogen treatment systems, involving preconcentration of heavy oil material in one or more suspension-phase reactors using a colloidal or molecular catalyst and further hydrogen treatment of the concentrated material in one or more fixed layer reactors using a supported porous catalyst. The colloidal or molecular catalyst is formed in situ by directly mixing a catalyst precursor composition with heavy oil material and raising temperature of the material to temperature above decomposition point of the catalyst precursor composition. Asphaltene and other hydrocarbon molecules which are in any case are too large for diffusion into pores of the fixed bed catalyst may be impregnated by the colloidal or molecular catalyst. One or more suspension-phase reactors may be made and placed upstream from one or more fixed layer reactors of the existing fixed layer hydrogen treatment system and/or converted from one or more existing fixed layer reactors.